1,3,4-thiadiazol-5-one-yl-ureas

ABSTRACT

1,3,4 - THIADIAZOL-5-ONE-2-YL-UREAS, I.E. 1-(4&#39;&#39;-(OPTIONALLY ALKYL, AKOXY-ALKYL, CYCLOALKYL, ALKYL-CYCLOALKYL, CYCLOALKENYL, TETRAHYDRONAPHTHYL, FLUORENYL, PHENYL-ALKYL, NAPHTHYL-AKYL, DIPHENYL-METHYL, TRIPHENYL-METHYL, CHLOROBENZYL, ALKYL-PHENYL-ALKYL, ALKOXY-BENZYL, NITRO-BENZYL, CYANOBENZYL, TRIFLUOROMETHYL-BENZYL, DIALKYL-AMINO-BENZYL, PHENYL, NAPHTHYL, HALO-PHENYL, ALKYL-PHENYL, ALKYL-PHENYL, NITRO-PHEN CYCANO-PHENYL,, TRIFLUOROMETHYL-PHENYL, ALKYL-CHLOROPHENYL, TRIFLUOROMTHYL-CHLORO-PHENYL, AND FURFURYL SUBSTITUTED)-1&#39;&#39;,3&#39;&#39;,4&#39;&#39;-THIADIAZOL-5&#39;&#39;-ONE-2&#39;&#39;-YL)-1-(OPTIONALLY ALKYL, AKENYLAND ALKOXY-ALKYL SUBSTITUTED)-3-(OPTIONALLY ALKYL AND ALKENYL SUBTITUTED)-3-(ALIPHATIC AND ALKOXY)-UREAS AS WELL AS THE THIONE AND THIOUREA ANOLOGUES THEREOF WHICH POSSESS HERBICIDAL PROPERTIES, AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent 3,801,589 1,3,4-THIADIAZOL--0NE-YL-UREAS KlausSasse and Ludwig Eue, Cologne-Stammheim, and Helmuth Hack,Cologne-Buchheim, Germany, assignors to Bayer Aktiengesellschaft,Leverkusen, Germany No Drawing. Continuation-impart of application Ser.No. 204,307, Dec. 2, 1971, which is a continuation-in-part ofapplications Ser. No. 817,417, Apr. 17, 1969, and Ser. No. 16,937, Mar.5, 1970, all now abandoned. This application Feb. 8, 1972, Ser. No.224,626 Claims priority, application Germany, Apr. 19, 1968, P 17 70236.2; Mar. 22, 1969,P 19 14 629.3 Int. Cl. C0711 91/62 US. Cl. 260-3063D 5 Claims ABSTRACT OF THE DISCLOSURE 1,3,4 thiadiazol-5-one-2-yl-ureas,i.e. 1-[4'-(optionally alkyl, alkoxy-alkyl, cycloalkyl,alkyl-cycloalkyl, cycloalkenyl, tetrahydronaphthyl, fluorenyl,phenyl-alkyl, naphthyl-alkyl, diphenyl-methyl, triphenyl-methyl,chlorobenzyl, alkyl-phenyl-alkyl, alkoXy-benzyl, nitro-benzyl,cyanobenzyl, trifluoromethyl-benzyl, dialkyl-amino-benzyl, phenyl,naphthyl, halo-phenyl, alkyl-phenyl, nitro-phenyl, cyano-phenyl,trifluoromethyl-phenyl, alkyl-chlorophenyl,trifluoromethyl-chloro-phenyl, and furfuryl substituted) -1',3,4'-thiadiazol-5 '-one-2-yl] 1- [optionally alkyl, alkenyl andalkoxy-alkyl substituted1-3-[optionally alkyl and alkenylsubstituted]3-[aliphatic and alkoxy]-ureas as well as the thione andthiourea analogues thereof which possess herbicidal properties, andwhich may be produced by conventional methods.

This application is a continuation-in-part of application Ser. No.204,307, filed Dec. 2, 1971, now abandoned, which in turn is acontinuation-in-part of application Ser. No. 817,147, filed Apr. 17,1960, now abandoned; it is also a continuation-in-part of applicationSer. No. 16,937, filed Mar. 5, 1970, now abandoned.

The present invention relates to and has for its objects the provisionof particular new 1,3,4-thiadiazol-5-one-2- yl-ureas, i.e.1-[4'-(optiona1ly alkyl, alkoxy-alkyl, cycloalkyl, alkyl-cycloalkyl,cycloalkenyl, tetrahydronaphthyl, fluoroenyl, phenyl-alkyl,naphthyl-alkyl, diphenyl-methyl, triphenyl-methyl, chloro-benzyl,alkyl-phenyl-alkyl, alkoxy-benzyl, nitro-benzyl, cyano-benzyl,trifluoro-methylbenzyl, dialkyl-amino-benzyl, phenyl, naphthyl,halophenyl, alkyl-phenyl, nitro-phenyl, cyano-phenyl,trifluoromethyl-phenyl, alkyl-chloro-phenyl,trifiuoromethylchloro-phenyl, and furfurylsubstituted)-1',3,4'-thiadiazol- 5'-one-2-yl]-l-[optionally alkyl,alkenyl and alkoxy-alkyl substituted]-3-[optionally alkyl and alkenylsu'bstituted]-3- [aliphatic and alkoxy]-ureas as well as the thione andthiourea analogues thereof, which possess valuable, especiallyselective, herbicidal properties, active compositions in the form ofmixtures of such compounds with solid and liquid dispersible carriervehicles, and methods for producing such compounds and for using suchcompounds in a new way, especially for combating weeds, undesiredplants, and the like, with other and further objects becoming apparentfrom a study of the within specification and accompanying examples.

It is already known that 1,3-thiazol-2-yl-ureas, for example 1 [5 methyl1',3'-thiazol-2'-yl]-3-methyl-urea (A), can be used as herbicidallyactive compounds (compare Belgian Pat. 679,138).

3,801,589 Patented Apr. 2, 1974 It has now been found, in accordancewith the present invention, that the particular new 1,3,4thiadiazolonylureas of the formula RNTI R: Y n

l X- -N -N -\S RIII in which R is hydrogen;

alkyl of 1-13 carbon atoms;

alkoxy-alkyl having 1-4 carbon atoms in the alkoxy moiety and 1-4 carbonatoms in the alkyl moiety;

cycloalkyl of 3-12 ring carbon atoms;

alkyl-cycloalkyl having 1-4 carbon atoms in the alkyl moiety and 5-5ring carbon atoms in the cycloalkyl moiety;

cycloalkenyl;

tetrahydronaphthyl;

phenyl-alkyl having 1-4 carbon atoms in the alkyl moiety;

naphthyl-alkyl having 1-4 carbon atoms in the alkyl molety;

diphenyl-methyl;

triphenyl-methyl;

chloro-substituted benzyl;

alkyl-phenyl-alkyl having 1-4 carbon atoms in each corresponding alkylmoiety;

alkoxy-benzyl having l-4 carbon atoms in the alkoxy moiety;

nitro-benzyl;

cyano-benzyl;

trifluoromethyl-benzyl;

dialkyl-amino-benzyl having 1-4 carbon atoms in each alkyl moiety;

phenyl;

naphthyl;

halo-substituted phenyl;

alkyl-phenyl having 1-4 carbon atoms in the alkyl moiety;

nitro-phenyl;

cyano-phenyl;

trifiuoromethyl-phenyl;

alkyl-chloro-phenyl having 1-4 carbon atoms in the alkyl moiety;

trifiuoromethyl-chloro-phenyl; and

furfuryl;

R is

hydrogen;

alkyl of 1-4 carbon atoms;

alkenyl of 2-4 carbon atoms; and

alkoxy-alkyl having 1-4 carbon atoms in the alkoxy moiety and 1-4 carbonatoms in the alkyl moiety;

R" is hydrogen;

alkyl of 1-3 carbon atoms; and

alkenyl of 2-3 carbon atoms; and

R' is aliphatic of 1-4 carbon atoms; and

alkoxy of 1-4 carbon atoms; and X and Y are oxygen or sulfur,

exhibit strong herbicidal, in particular selective herbicidal,properties.

It has been furthermore found, in accordance with the present invention,that processes for the particular new compounds of Formula I above maybe provided, which comprise:

[a] Reacting a carbamic acid halide of the formula in which R and R' arethe same as defined above, and Hal is chlorine or bromine with an amineof the formula H HN R (III) in which R" and R' are the same as definedabove, or

[b] Reacting a 2-amino-1,3,4-thiadiazol-5-one of the formula I R X1 inwhich R and R are the same as defined above NH (I with an isocyanate orthioisocyanate of the formula R represents hydrogen;

alkyl hydrocarbon of 1-13 carbon atoms such as methyl, ethyl, nandiso-propyl, n-, iso-, sec.- and tert.-butyl, amyl, iso-amyl, hexyl,iso-hexyl (S-methyl-pentyl), 1,2,2-trimethyl-propyl, heptyl,l-n-propyl-butyl, octyl, 2-ethyl-hexyl, nonyl, decyl, undecyl, dodecyl,tridecyl, l-methyl-dodecyl, and the like, i.e. C alkyl, especialy i-s1-6 or 1-14 y alkoxy-alkyl having 1-4 carbon atoms in the alkoxy moietyand 1-4 carbon atoms in the alkyl moiety such as methoxy, ethoxy, nandiso-propoxy, n-, iso-, sec.- and tert.-butoXy-, and the like, -methyl,ethyl, nand isopropyl, n-, iso-, sec.- and tert.-butyl, and the like,i.e. C alkoxy-C alkyl, especially C alkoxy- C alkyl;

cycloalkyl of 3-12 ring carbon atoms such as cyclo-propyl, pentyl,-hexyl, -heptyl, -octyl, -nonyl, -decyl, -undecyl, -dodecyl, and thelike, i.e. C cycloalkyl, especially C or C cycloalkyl, i.e. cyclopropyland cyclohexyl;

alkyl-cycloalkyl having l-4 carbon atoms in the alkyl moiety and 5-6ring carbon atoms in the cycloalkyl moiety such as methyl totert.-lgutylinclusive as defined above, and the like, -cyclopentyl,cyclohexyl, and the like, i.e. 2-, 3- and 4- (C alkyl)- C cycloalkyl,especially C alkyl- C cycloalkyl, and more especially 3- or 4-(C or Calkyl)- C cycloalkyl e.g. cyclohexyl);

cycloalkenyl such as cyclohexenyl, and the like;

tri alkyl-cyclohexenyl having 1-2 carbon atoms in each alkyl moiety suchas 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-tri (same and mixed)methyl ethyl, and the like, -cycloheX-1,2 and 3-enyl, i.e. -tri Calkyl-cyclohexenyl, especially 3,4,5-tri C alkyl-cyclohexenyl, moreespecially 3,4,5-tri 0 alkyl-cyclohex-1,2 and 3-enyl, and mostespecially 3,4,5-trimethyl-cycloheX-2- enyl;

tetrahydronaphthyl such as l,2,3,4-tetrahydronaphthyl,

and the like;

phenyl-alkyl having 1-4 carbon atoms in the alkyl moiety such as phenyl--methyl to tert-butyl inclusive as defined above, and the like, i.e.phenyl-(3 alkyl, including benzyl, phenyl- -eth-1 and 2-yl, prop-1,2 and3-yl, but-1,2,3 and 4-yl, and the like, especially phenyl- C1 .3 01(31-2 naphthyl-alkyl having 1-4 carbon atoms in the alkyl moiety such asnaphthyl- -methyl to tert.-buty1 inclusive as defined above, and thelike, i.e. naphthyl-C alkyl, including aand B-naphthyl- -methyl, eth-land 2-yl, prop-1,2 and 3-yl, but-1,2,3 and 4-yl, and the like,especially aand p-naphthyl-C or (3 alkyl;

diphenyl-methyl;

triphenyl-methyl;

chloro-substituted benzyl such as mono to tri chloro substituted benzyl,including 2, 2- and 4-mono, 2,3-, 2,4- 2,5-, 2,6-, 3,4- and 3,5-di, and2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5- tri chloro substitutedbenzyl, especially 4-chloro, 2,4-dichloro and 2,4,5-trichlorosubstituted benzyl, and the like;

alkyl-phenyl-alkyl having 1-4 carbon atoms in each alkyl moiety such asmethyl to tert.-butyl inclusive as defined above, and the like, -phenyl--methyl to tert.-butyl inclusive as defined above, and the like, i.e. 2,3- and 4-(C alkyl)-phenyl-C alkyl, especially 4-(C alkyl)-phenyl-C or Cialkyl;

alkoxy-benzyl having 1-4 carbon atoms in the alkoxy moiety such asmethoxy to tert.-butoxy inclusive as defined above, and the like,-benzyl, i.e. 2, 3- and 4-(C -alkoXy)-benzyl, especially 4-(C or Calkoxy)- benzyl, and the like;

nitro-benzyl such as 2-, 3- and 4-nitro-benzyl, especially3-nitro-benzyl;

cyano-benzyl such as 2, 3- and 4-cyano-benzyl, especially4-cyano-benzyl;

trifluoromethyl-benzyl such as 2, 3- and 4-trifluoromethyl-benzyl,especially 4-triflu0romethyl-benzyl;

dialkyl-amino-benzyl having 1-4 carbon atoms in each alkyl moiety suchas di (same and mixed) methyl to tert.-butyl inclusive as defined above,and the like,

-amino-benzyl, i.e. di-C lalkyl-amino-benzyl, especial- 1y 2, 3- and4-(di-C or C alkyl)-amino-benzyl, and more especially 4-(di-C or Calkyl, preferably methyl)-amino-benzyl;

phenyl;

naphthyl such as Otand B-naphthyl, and the like;

[halo-substituted phenyl such as 2, 3- and 4-mono and 2,3-, 2,4-, 2,5,2,6-, 3,4- and 3,5- di (same and mixed) chloro, bromo, iodo and fluoro--phenyl, and the like, especially mono and di chloro-phenyl,bromo-phenyl, iodo-phenyl and fiuorophenyl, and more especially 2, 3-and 4-chloro-phenyl, 4-bromo-phenyl, 4-iodo-phenyl, 4-fiuoro-phenyl, andthe like;

alkyl-phenyl having 1-4 carbon atoms in the alkyl moiety such as methylto tert.-butyl inclusive as defined above, and the like, -phenyl, i.e.2, 3- and 4-(C alkyl)- phenyl, especially C alkyl-phenyl, moreespecially methyl-phenyl, and most especially 4-methyl-phenyl;

nitro-phenyl such as 2-, 3- and 4-nitro-phenyl, especially2-nitro-phenyl;

cyano-phenyl such as 2-, 3- and 4-cyano-phenyl, especially4-cyano-phenyl;

trifiuoromethyl-phenyl such as 2-, 3- and 4-trifluoromethyl-phenyl,especially 4-trifluoromethy1-phenyl;

alkyl-chloro-phenyl having 1-4 carbon atoms in the alkyl moiety such asmethyl to tert.-butyl inclusive as defined above, and the like,-chloro-phenyl, i.e. C alkylchloro-phenyl, including 2-(C or Calkyl)-3,4,5 and 6-chloro-phenyl, 2-chloro-3,4,5 and 6-(C or Calkyl)-phenyl, 3-(C or C alkyl)- 4 and S-chloro-phenyl, and 3-chloro-4and 5-(C or C alkyl)-phenyl, especially 3-chloro 4 (C alkyl)- phenyl,and more especially 3-chloro-4-methyl-phenyl, and the like;

trifluoromethyl-chloro-phenyl such as 2-trifiuoromethyl- 3,4,5 and6-chloro-phenyl, 2-chloro-3,4,5 and 6-trifiuoromethyl-phenyl,3-trifluoromethyl-4 and 5-cl1lorophenyl, and 3-chloro-4 andS-trifluoromethyl-phenyl, especially 2-chloro-4-trifiuoromethyl-phenyl,and the like; and

furfuryl;

R represents hydrogen;

alkyl of 1-4 carbon atoms such as methyl to tert.-butyl inclusive asdefined above, and the like, i.e. C alkyl, especially C alkyl;

alkenyl of 2-4 carbon atoms such as vinyl, Z-methylvinyl, allyl, but-1,2and 3-enyl, and the like, i.e. C alkenyl, especially alkenyl, and moreespecially 0;, alkenyl, i.e. allyl; and

alkoxy-alkyl having 1-4 carbon atoms in the alkoxy moiety and 1-4 carbonatoms in the alkyl moiety, such as methoxy to tert.-butoxy inclusive asdefined above, and the like, -methyl to tert.-butyl inclusive as definedabove, and the like, i.e. C alkoxy-C alkyl, especially 0 alkoxy-C alkyl,and the like;

R" represents hydrogen;

alkyl of 1-3 carbon atoms such as methyl, ethyl, nand iso-propyl, andthe like, i.e. C alkyl, especially C alkyl; and

alkenyl of 2-3 carbon atoms such as vinyl, prop-1 and -2-enyl, and thelike, i.e. C alkenyl, especially C alkenyl, and more especially allyl;and

R' represents aliphatic hydrocarbon of 1-4 carbon atoms including: alkylof 1-4 carbons such as methyl to tert.-butyl inclusive as defined above,and the like, i.e. C alkyl, especially C alkyl; alkenyl of 2-4 carbonatoms such as vinyl, prop-1 and -2-enyl, but-1,2 and 3-enyl, and thelike, i.e. C alkenyl, especially C alkenyl, more especially C alkenyl,and most especially allyl; and alkynyl (i.e. alkinyl) of 2-4 carbonatoms such as acetylenyl, prop-l and 2-ynyl, but-1,2 and 3-ynyl, and thelike, i.e. C alkynyl, especially C alkynyl, more especially C alkynyl,i.e. propynyl, and most especially prop-2-ynyl; and alkoxy of 1-4 carbonatoms such as methoxy to tert.butoxy inclusive as defined above, and thelike, i.e. C alkoxy, and especially C alkoxy. Preferably, R is C alkyl;or C cycloalkyl, especially cyclohexyl; or phenyl; or chloro-phenyl;especially mono and di chloro-phenyl; or C alkyl-phenyl, especiallymethyl-phenyl; or chloro-trifluoromethyl-phenyl; R is C alkyl,especially C alkyl; R" is hydrogen; or C alkyl, especially C alkyl; andR is C alkyl, especially C alkyl; or C alkenyl, especially allyl.

The reaction course of the process [a] can be represented as followswhen 2-[(N-methyl-N-chlorocarbonyl)-amino]-4-cyclohexyl-1,3,4-thiadiazoline-5-one and methylamine are usedas starting materials:

| CH: 0% J-N-CO-Cl+ HNHCH;

The course of the reaction of process variant a can be represented asfollows when the reactants are 2-(N- methyl N chlorocarbonylamino) 4isopropyl-l,3,4- thiadiazoline-thione-(S) and methylamine:

(IIb) The starting carbamic acid halides of Formula II above are not yetknown. These starting compounds can, however, be prepared in simplemanner when the appropriate 1,4-disubstituted thiosemicarbazides arereacted in inert organic solvents, such as hydrocarbons or chlorinatedhydrocarbons, with at least 2, preferably 2 to 4, mols of phosgene orthiophosgene per mol of thiosemicarbazide, at a temperature from about-20 to 200 C. (see German patent application F 54 220 IVd/ 12p; 5.12.1967). They can also be prepared in simple manner by reactingsuitably substituted 2-amino-l,3,4-thiadiazoline-5-(thi)ones in inertorganic solvents, such as hydrocarbons or chlorinated hydrocarbons, withat least the equimolar amount of phosgene or thiophosgene attemperatures from about 20 to +200 C.

In the following, four typical examples are given for the preparation ofstarting carbamic acid chlorides of the Formula II above.

[a Preparation of 2-[(N-chlorocarbonyl-N-methyl)- amino]-4-phenyl-1,3,4-thiadiazoline-5-one 181 g. (1 mol) of1-phenyl-4-methyl-thiosemicarbazide are suspended in 700 ml. ofchlorobenzene. Phosgene is gradually introduced at room temperature, thetem perature rising to 40 to 45 C. At the same time the suspensioninitially thickens and then later thins out. After subsidence of theexothermic effect, the mixture is heated by external means in order tomaintain a temperature of 40 to 45 C. After about 220 g. of phosgene(2.2 mols) have been introduced, a clear solution has formed. Heating isslowly continued up to C. in a weak stream of phosgene and thistemperature is maintained for a further hour. The solution is evaporatedin a vacuum. There remains a residue of 2-[(N-chlorocarbonyl-N-methyl)-amino]-4-phenyl-1,3-4-thiadiazoline 5 one in practicallyquantitative yield. Recrystallized from carbon tetrachloride, thepurified product is obtained in 82% yield. M.-P. C.

[a Preparation of 2-[(N-chlorocarbonyl-N-methyl)-amino]-4-propyl-1,3,4-thiadiazoline-5-one 147 g. (1 mol) ofl-propyl-4-methyl-thiosemicarbazide are dissolved in 600 ml. ofchloroform. About 220 g. (2.2 mols) of phosgene are introduced at roomtemperature, the temperature rising to about 40 C. A colorlessprecipitate which temporarily formed re-dissolves in the further courseof the reaction. After subsidence of the exothermic effect, the solutionis heated at boiling point for about 1 hour in a weak stream of phosgeneand then evaporated in a vacuum. There remains, in practicallyquantitative yield, a residue which gradually crystallizes and fromwhich 2-[(N-chlorocarbonyl-N-methyl)-amino]-4-propyl-1,3,4thiadiazoline-5-one is obtained in pureform in 86% yield by recrystallization from ligroin. M.P. 34-36 C.

[a Preparation of 2-(N-chlorothiocarbonyl-N-methylamino) -4-phenyll 3,4-thiodiazoline-5-one 207 g. (1 mol) of2-methylamino-4-phenyl-1,3,4-thiadiazoline-S-one are suspended in 600ml. of chloroform. To this suspension are added dropwise at roomtemperature 115 g. (1 mol) of thiophosgene. The mixture is graduallyheated to the boil and then boiled until hydrogen chloride ceases toescape. After evaporation of the solvent, the above-mentioned compoundremains in practically quantitative yield. Recrystallized fromcyclohexane it has a melting point of 79 to 80 C.

[a Preparation of 2-(N-chlorocarbonyl-N-ethylamino)-4-isopropyl-l,3,4-thiadiazoline-5-thione (A) Z-ethylamino 4 isopropyl1,3,4 thiadiazoline- S-thione:

To a suspension of 161 g. (1 mol) of l-isopropyl-4-ethylthiosemicarbazide in 500 ml. of chloroform 115 g. (1 mol) ofthiophosgene are added dropwise at room temperature, with cooling. 7

After the exothermic reaction has ended, the mixture is gradually heatedto the boil and boiled until the color of the thiophosgene hasdisappeared and hydrogen chloride ceases to escape. Filtration fromsmall amounts of the insoluble constituents is effected and the filtrateis evaporated in vacuo. The residue is recrystallized from cyclohexaneand recovered as the2-ethylamino-4-isopropyl-1,3,4-thiadiazoline-5-thione. Yield: 179 g.(88% of theory); M.P. 84.

(B) 2- N-chlorocar-bonyl-N-ethylamino) -4-isopropyl-1,3,4-thiadiazoline-5-thione:

Into a solution of 179 g. (0.88 mole) of the preceding product of (A) in500 ml. of chloroform, 96 g. (0.96 mole) of phosgene are introduced atroom temperature, With slight cooling. The mixture is heated to the boilgradually in a weak stream of phosgene, and boiling is effected for afurther hour under reflux. The crystals remaining after evaporation ofthe solvent are recrystallized from cyclohexane. Yield: 210 g. (90%) oftheory); M.P. 115-116".

When carrying out process variant [a], it is preferable to work underthe following conditions:

The reaction can be carried out in the presence of a solvent (the termsolvent as used herein includes mere diluents). As solvents, all inertorganic solvents are suitable, and include: aliphatic and aromatichydrocarbons, which may be chlorinated, such as benzene, toluene,chlorobenzene, methylene chloride, chloroform and carbon tetrachloride;ketones, such as acetone and cyclohexanone; ethers, such as diethylether, dioxan and tetrahydrofuran; and the like; and mixtures of two ormore of these solvents. However, the work can also be carried out inaqueous suspensions which either contain only water, water and awater-soluble inert organic solvent, or water and a water-insolubleinert organic solvent.

Acid-binding agents are preferably added in order to bind the halogenhydride which .forms. As acid binding agents, the amines used for thereaction may function when double the equimolar amount, with referenceto the acid halide, is used. Other acid-binding agents may, hoW- ever,also be used, for example inorganic bases, such as alkali metalhydroxides and alkaline earth metal hydroxides, alkali met l carbona sand alkal e earth metal carbonates, or organic bases, such as tertiaryamines, for example triethylamine, N,N-dimethylaniline and pyridine; andthe like.

The reaction temperatures can be varied Within a fairly wide range. Ingeneral, the reaction is carried out at from substantially between 0 to0., preferably from about 10 to 40 C.

Process variant [a] is preferably carried out using equimolar amounts ofthe reactants.

The reaction is carried out in the usual manner, as is the working up ofthe reaction mixture, .for example by filtration, concentration andcrystallization.

When starting with 2-methylamino-4-phenyl-1,3,4- thiadiazol-S-one andmethyl isocyanate, the process variant [b] can be represented asfollows:

I CH3 Oi LN-CO-NHCHQ (IVb) (Va) Only a few of the startingamino-1,3,4-thiadiazolones of Formula IV above are known. Those startingthiadiazolones which are new can be prepared in an analogous manner tothose that are known:

(1) They can be obtained when 1,4-disubstituted thiosemicarbazides arereacted with about equimolar proportions of (thio)phosgene (compare forexample Five-Membered Heterocyclic Compounds With Nitrogen and Sulfur orNitrogen, Sulfur and Oxygen, pages 153-173 (1952), in the series: A.Weissberger, The Chemistry of Heterocyclic Compounds, IntersciencePublishers, New York). Preparation of 2-ethylamino4-isopropyl-1,3,4-thiadiazoline-S-thione proceeds, for example, startingfrom l-isopropyl-4-ethylthiosemicarbazide, according to the followlng:

The reaction is preferably carried out in an inert solvent, such as ahydrocarbon, for example, kerosene, benzene, toluene; a chlorinatedhydrocarbon, for example, methylene chloride, chloroform, carbontetrachloride; or an ether such as diethyl ether or glycoldimethylether, at a temperature from -10 to 100 C., preferably 0 to 30 C.

(2) (a) The 2-amino-1,3,4-thiadiazol-5-one unsubstituted in 5-positigncan be prepared by heating l-carbamo- 9 yl-2-thiocarbamoyl-hydrazine inconcentrated hydrochloric acid [Chem. Ber. 29, 2506 (1896); J. Ind.Inst. Sci. 16A, 11 (1933); J. Pharm. Soc. Japan 72, 1533 (1952)].

(b) This substance can also be prepared by reaction of2-thiocarbamoyl-hydrazine-carboxylic acid ethyl ester with aceticanhydride and subsequent acidic splitting up of the acetyl derivativeinitially formed (compare Soc. 1958, 1508).

(3) A quite general process for the preparation of theZ-amino-l,3,4-thiadiazol-5-ones comprises treating the appropriate2-halocarbonylamino compounds of Formula II above in the presence of aninert organic solvent, for example acetone, at low temperatures, forexample for to 20 C., with aqueous solution of alkali, for exampleaqueous solution of sodium hydroxide, the chlorocarbonyl radical beingsplit off.

Isolation takes place in the usual manner, for example by neutralizationof the reaction mixture and filtering off of the reaction product.

In the following, a typical example is given for the preparation of astarting amino-1,3,4-thiadiazolone of Formula IV above.

[b Preparation of 2-a]lylamino-4-phenyl-1,3,4- thiadiazol-S-one 45 g.2-[(N-allyl-N-chlorocarbonyl)-amino] 4 phenyl-1,3,4thiadiazol-5-one aredissolved in 250 ml. acetone. A solution of 18 g. sodium hydroxide in100 ml. of water is added dropwise, with cooling (temperature 20 0.).The mixture is then stirred for 1 hour at room temperature. A further500 ml. of water are added, and neutralization is eifected by theaddition of small amounts of hydrochloric acid. The separated reactionproduct is filtered off with suction, dried, and recrystallized fromwhite spirit. Yield: 30 g.; M.P.: l03105 C.

The isocyanates of Formula V above are known.

The preferred conditions for the process variant [b] are as follows:

The reaction can be carried out in the presence of a solvent. In thiscase, the same solvents as suitable for variant [a] as noted above maybe used. It is, however, also possible to carry out the reaction in themolten state without diluents or solvents.

The reaction temperature can be varied within a fairly wide range. Ingeneral, they are from substantially between about 0 to 150 C.

In order to accelerate the reaction, tertiary amines, such astriethylamine, tributylamine, tri-ethylenediamine, tin (II)octoate, andthe like, may be added in small amounts. It is also possible to carryout the reaction from the beginning in a tertiary amine, for example,pyridine.

When carrying out the reaction variant [b], approximately equimolaramounts of the starting materials are preferably used. Working up maytake place in the usual manner.

Typical examples of the particular new ureas according to the presentinvention are mentioned in the following Table A.

TABLE A TABLE A-Continued EXEMPLARY COMPOUNDS OF THE GENERAL FORMULAthlourea. 180..-- 1-[4-ethyl-1, 3, 4-thladiazolone-(5)-yl-(2)]-1,3-dlrnethylthiourea.

Advantageously, the instant thiadiazolonyl-ureas exhibit a strongherbicidal potency and can therefore be used as weed killers. By weedsare meant in the widest sense all plants which grow in places where theyare not desired. Whether the active compounds according to the presentinvention act as total or selective herbicidal agents depends on theamount of active compound applied.

The active compounds according to the present invention can be used inthe case of, for example, the following plants: dicotylendons, such asmustard (Sinapis), cress (Lepidium), cleaver (Galium), common chickweed(Stellaria), mayweed (Matricaria), smallflower Galinsoga (Galinsoga),fathen (Chemopodium), stinging nettle (Urtica), groundsel (Senecio),cotton (Gossypium), beets (Beta), carrots (Daucus), beans (Phaseolus),potatoes (Solanum), coffee (Coffea); monocotyledons, such as timothy(Phleum), bluegrass (Poa), fescue (Festuca), goosegrass (Eleusine),foxtail (Setaria), ryegrass (Lolium), cheat (Bromus), barnyard grass(Echinochloa), maize (Zea), rice ('Oryza), oats (Avena), barley(Hordeum), wheat (Triticum), millet (Panicum), sugar cane (Saccharum);and the like.

The instant thiadiazolonyl-ureas are preferably used as selectiveherbicides. Such active compounds exhibit a good selectivity in, forexample, cotton, cereals such as oats and wheat, and carrots.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert pesticidal diluents or extenders, i.e. conventionalpesticidal dispersible carrier vehicles, such as solutions, emulsions,suspensions, emulsifiable concentrates, spray powder, pastes, solublepowders, dusting agents, granules, etc. These are prepared in knownmanner, for instance by extending the active compounds with conventionalpesticidal dispersible liquid diluent carriers and/or dispersible solidcarriers optionally with the use of carrier vehicle assistants, e.g.conventional pesticidal surface-active agents, including emulsifyingagents and/r dispersing agents, whereby, for example, in the case wherewater is used as diluent, organic solvents may be added as auxiliarysolvents.

The following may be chiefly considered for use as conventional carriervehicles for this purpose: inert dispersible liquid diluent carriersincluding inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, etc.), halogenated, especially chlorinated,aromatic hydrocarbons (e.g. chloro-benzenes), parafiins (e.g. petroleumfractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride,etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.),ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amines(e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.),sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone,etc.), and/or water; as well as inert dispersible finely divided solidcarriers such as ground natural minerals (e.g. kaolins, alumina, silica,chalk, i.e. calcium carbonate, talc, kieselguhr, etc.), and groundsynthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g.alkali silicates, etc.); whereas the following may be chiefly consideredfor uses as conventional carrier vehicle assistants, e.g. surface-activeagents, for this purpose: emulsifying agents, such as nonionic and/ oranionic emulsifying agents (e.g. polyethylene oxide esters of fattyacids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates,aryl sulfonates, etc., and especially alkyl aryl-polyglycol ethers,magnesium stearate, sodium oleate, etc.); and/or dispersingagents, suchas lignin, sulfite waste liquors, methyl cellulose, etc.

As will be appreciated by the artisan, the active compounds according tothe instant invention may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other herbicides, orfungicides, insecticides, bactericides, etc., if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1 and 95% by weight,and preferably 0.5 and by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.005-1.0%, preferably0.01- 0.5%, by weight of the mixture. Thus, the present inventioncontemplates overall compositions which comprise mixtures of aconventional dispersible carrier vehicle such as (1) a dispersible inertfinely divided carried solid, and/ or (2) a dispersible carrier liquidsuch as an inert organic solvent and/ or water preferably including asurface-active amount of a carrier vehicle assistant, e.g. asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0.005%, andpreferably 0.01- 95 by weight of the mixture.

In particular, the amount of active compound per unit area variesaccording to the purpose intended, i.e. the effect desired, and the modeof application. In general, substantially between about 0.25-20 kg. ofactive compound per hectare are applied, preferably between about 0.5-1Okg. per hectare.

Furthermore, the concentration of the active compound in the usualaqueous preparations and in the case of postemergence application is, ingeneral, substantially between about (LOGS-1.0%, and preferably betweenabout 0.01- 0.5%, by weight, as aforesaid.

The active compounds can also be used in accordance with the well-knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g. average particle diameter of from 50- microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufiicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95 by weight of the activecompound or even the 100% active substance alone, e.g. about 20-100% byweight of the active compound.

While the active compounds can be used according to the pre-emergencemethod, they are also particularly effective when used according to thepost-emergence method.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling undesired plants, e.g. weeds and thelike, which comprise applying to at least one of (a) such weeds and (b)their habitat, i.e. the locus to be protected, a herbicidally effectlveor toxic amount of the particular active compound of the invention aloneor together with a carrier vehicle as noted above. The instantformulations or compositions are applied in the usual manner, forexample by spraying,

atomizing, scattering, dusting, watering, sprinkling, and the like,whether for preemergence application to the soil or post-emergenceapplication to the weeds.

It will be realized, of course, that in connection with thepre-emergence use of the instant compounds as well as the post-emergenceuse thereof, the concentration of the particular active compoundutilized in admixture with the carrier vehicle will depend upon theintended application and may be varied within a fairly wide rangedepending upon the weather conditions, the purpose for which the3,801,589 15 16 e.g. as total or only selective Seeds of the test plansare sown in normal soil and, after 24 hours, watered with the givenactive compound preparation. It is expedient to keep constant the amountof water per unit area. The concentration of the active 5 compound inthe preparation is of no importance, only the amount of active compoundapplied per unit area being decisive. After three weeks, the degree ofdamage to the test plants is determined and characterized by the values0-5, which have the following meaning 10 0 no effect 1 slight damage ordelay in growth ight acetone 2 marked damage or inhibition of growthEmulsifier: 1 part by weight alkylarylpolyglycolether 3 heavy damage andonly deficient development or only 50% emerged plants partiallydestroyed after germination or only 25% emerged 5 plants completely deador not emerged.

The particular active compounds tested, the amounts applied and theresults obtained can be seen from the 20 following Table 1:

TABLE 1.PRE-EMERGENCE TEST Concen- Echino- Cheno- Sin- Cottration chloapodium apls Oats ton Wheat Stellarla Galinsoga Matrlcarla is used,

in special cases, it is possible to go above EXAMPLE 1 1 part by weightof such active com- Therefore,

The following examples illustrate, without limitation,

Solvent: 5 parts by we To produce a suitable preparation of theparticular 5 4 4 32 000 000 000 210 100 100 555 543 54 3 100 100 210 200442 554 100 000 3 L *3 z a a. a a a. a. a. H 432 553 553 {W32 4 3 583321 555 555 55 554 554 555 543 543 555 544 54 4 H 4 a a. a .r a a a. H055 055 055 055 055 055 055 055 055 055 055 055 055 055 055 055 055 0551 a I a a o n I u l n n 1 l l n c 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 21 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 m J H N 4 a H m h S C/ N H W C 0 0 aw mi t a \l 5 6 9 \J 2 6 7 A 5 8 8 9 m o d 0 w m M w w u 0 0 m n u u m 6 6active compoun herbicidal effect, and the plants which are to becontrolled or protected.

or below the aforementioned concentration ranges.

the herbicidal activity of the particular active compounds of thepresent invention.

Pre-emergence test active compound pound is mixed with the stated amountof solvent, the stated amount of emulsifier is then added and theresulting concentrate is thereafter diluted with water to the desiredfinal concentration.

Active compound Eee footnote at end of table.

Tas a-1.- RE-E ERGENcE TEST Concen- Eehino- Cheno- Sin- Cot- Activecompound tration chloa podium, apis Oats ton Wheat Stellaria GalinsogaMatricaria 145 20 5 5 5 a 4 a 5 5 s 10 4 5 5 3 3 1 5 5 5 5 3 4-5 4 2 3 05 5 5 (13g) 20 5 5 5 a 2 2 5 5 5 10 4 5 4 2 1 1 5 5 5 5 3 5 l 3 1 0 0 55 5 Active compound in kgJhectare.

EXAMPLE 2 Post-emergence test:

Solvent: 5 parts by weight acetone Emulsifier: 1 part by weightalkylarylpolyglycolether To produce a suitable preparation of theparticular active compound, I part by weight of such active compound ismixed with" the stated amount of solvent,- the stated amount ofemulsifier is then added and the resulting concentrate is thereafterdiluted with water to'the desired final concentration.

Test plants whichhave'a height of about 5-15 cm. are sprayed with thegiven active compound preparation until just dew moist. After threeweeks, the degree of damage to the plants is determined andcharacterized by the values 0-5, which have the the following meaning:

0 no effect 1 a few slightly burnt spots 2 marked damage to leaves 3some leaves and parts of stalks partially dead 4 plant partiallydestroyed 5 plant completely dead.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 2:

TABLE 2.POST-EMERGENCE TEST Concen-

tra-

......................... tion Echino- Active compound )(known).

Ewen

Elli-HUI OIOIO! UNDER See footnote at end of table.

omen ewe-en 0mm more:

Chenoehloa podium Sinapls Galln- Stelsoga laria Matri- 03113 Col;-

Oats ton Urtica Wheat Mini TABLE 2.POST-EMERGENCE TEST.ContinuedConcentra- Eehino- Gheno- Sin- Galln- Stel- Matrl- Cot- Car- Aetivecompound tion chloa podium apis soga laria Urtiea caria Oats ton Wheatrots (31) 0.1 5 5 5 5 l5 5 5 4 3 5 5 0.05 5 5 5 5 5 5 5 2 2 4 5 0.025 55 5 5 5 5 4 0 0 3 5 (84) 0.1 5 5 5 5 5 5 5 5 5 5 5 0.05 5 5 5 5 5 5 5 55 5 5 0.025 5 5 5 5 5 5 5 4 5 5 5 (155) 5 5 5 5 5 5 5 4-5 B 4 1 2.5 5 55 5 5 5 4 5 3 0 1.25 4 5 5 4-5 4-5 5 3-4 4-5 2 0 145) 5 5 5 5 5 5 5 4 33 1 2.5 4-5 4-5 5 4 4 5 3 2 1 0 1.25 4 4 5 3 3 4-5 2 0 0 0 (138) 5 5 5 55 5 5 4 2 3 2 2.5 5 5 5 4-5 4 5 3 0 2 0 1.25 5 4 5 4 3 4 3 0 0 0 (142) 54-5 5 5 3 4 5 4 4 3 1 2.5 4 4-5 5 2 2 3 8-4 3 2 0 1.25 2 4 4 1 0 2 2 1 00 153) 5 5 5 5 5 l5 3. 1 5 1 2.5 5 5 5 4 4-5 2 0 4 0 1.25 4 4-5 5 3 4 10 3 0 39 5 5 4-5 5 5 5 2 3 4 0 2.5 4-5 4 5 5 5 0 0 3 0 1.25 3 3 5 4 5 00 3 0 1 Active compound in percent.

The following further examples are set forth to illustrate, withoutlimitation, the process for the production 65 of the particular newcompounds in accordance with the present invention.

EXAMPLE 3 [Reaction variant (b)] 70 20.7 g. (0.1 mol)2-methylamino-4-phenyl-1,3,4-thiadiazol-S-one are dissolved in m1. ofdimethyl formamide. After addition of a catalytic amount oftriethylenediamine, there are added dropwise at room temperature 5.7 g.(0.1 mol) of methyl isocyanate. The mixture is stirred for 1 hour at(room temperature, 1 hour at 35-40 C. and 1 hour at 70-75 0., cooling toroom temperature is effected, and the reaction product is precipitatedby addition of water. The product is dried and recrystallized frombutanol. Yield: 23.2. g. (88% of the theory) of 1-[4'-phenyl 1',3',4'thiadiazo1-5'-one-2'-yl]-1,3-dimethylurea, M-P- 197-198" C.

EXAMPLE 4 [Reaction variant (a)] i CH; O

26 g. (0.1 mol) of 2-(N-methyl-N-chlorocarbonylamino)-4-cyclohexyl-1,3,4-thiadiazolin-5-one are dissolved in 125 m1. ofacetone. .17 g. (0.22 mol) of a 40% aqueous methylamine solution areadded dropwise at room temperature, with stirring and cooling. Stirringis com tinued for 1 hour, 250 ml. of water are added and theprecipitated product is filtered oflf with suction. After drying, 24.8g. (92% of the theory) of 1-[4'-cyclohexyl-1,3',4'-thiadiazol-5-one-2'-yl]-1,3-dimethyl urea are obtained, M.P.196-198 C.

EXAMPLE 5 [Reaction variant (a)] 9.9 g. (0.22 mol) of dimethyl amine areintroduced at 20 to 25 0. into a solution of 22.2 g. (0.1 mol) of 2-(N-methyl N chlorocarbonyl-amino)-4-ethyl 1,3 thiadiazolin-S-one in 125 ml.benzene, with cooling. The mixture is stirred for 1 hour at roomtemperature, then washed twice with water, and the benzene solution isevaporated in a vacuum. There remains as residue 1-[4- ethyl 1,3,4'thiadiazo1-5'-one-2-yl] 1,3,3 trimethylurea in practically quantitativeyield. Recrystallized from white spirit, it melts at M.P. 6062 C.

EXAMPLE 6 To a suspension of 19.1 g. (0.1 mol) Z-(N-methyl-N-chlorocarbonylamino)-4-isopropyl 1,3,4 thiadiazoline- S-thio'ne in 125m1. acetone there are added dropwise at room temperature, with cooling,17 g. (0.22 mol) of a 407 aqueous methylamine solution. The clearsolution formed is, after completion of the exothermic reaction,

stirred for 1 hour at room temperature and then evaporated in vacuo. Thecrystals obtained after washing with water the residue which remains arefiltered 011 with suction and dried.

Yield: 22.4 g. (91% of the theory); M.P. 184-185 C. (toluene).

EXAMPLE 7 O S CH; CH; (139) 28.5 g. (0.1 mol) 2-(N-methyl-N-chlorothiocarbonylamino)-4-phenyl-1,3,4-thiadiazoline-5-oneare dissolved in 150 ml. benzene. 10 g. (0.22 mol) of gaseousdimethylamine are introduced at room temperature, with cooling. Themixture is stirred for one hour at room temperature, washed with water,dried over sodium sulphate and evaporated in vacuo. There remain 25.6 g.(87% of the theory) of crystals which, after reprecipitation fromether/ligroin, melt at 87 C.

EXAMPLE 8 S OH; (140) To a solution of 22.9 g. (0.1 mol)2-methylamino-4- cyclohexyl-1,3,4thriadiazoline-5-thione and 125 1111.benzene there are added dropwise at room temperature, after addition ofa catalytic amount of triethylenediamine, 5.7 g. (0.1 mol)methylisocyanate. The mixture is stirred for 1 hour at room temperature,1 hour at 35 to 40 C. and 1 hour at 70 to C. and then evaporated invacuo, the above-mentioned product remaining behind in practicallyquantitative yield; M.P. 189l90 C. (ethanol).

EXAMPLE 9 It will be appreciated that the instant specification andexamples are set forth by way of illustration and not limitation, andthat various modifications and changes may be made without departingfrom the spirit and scope of the present invention.

What is claimed is:

1. 1,3,4 thiadiazole one-2-yl urea of the formula ol lllats in which Ris selected from the group consisting of hydrogen, alkyl of 1-13 carbonatoms, alkoxy-alkyl having 1-4 carbon atoms in the alkoxy moiety and 1-4carbon atoms in the alkyl moiety, cycloalkyl of 3-12 ring carbon atoms,alkyl-cycloalkyl having 1-4 carbon atoms in the alkyl moiety and 5-6ring carbon atoms in the cycloalkyl moiety, cyclohexenyl,tetrahydronaphthyl, fluorenyl, phenyl-alkyl having 1-4 carbon atoms inthe alkyl moiety, naphthyl-alkyl having 1-4 carbon atoms in the alkylmoiety, diphenyl-methyl, triphenyl-methyl, chloro-substituted benzyl,alkyl-phenyl-al-kyl having 1-4 carbon atoms in each corresponding alkylmoiety, alkoxy-benzyl having 1-4 carbon atoms in the alkoxy moiety,nitro-benzyl, cyano benzyl, trifiuoromethyl benzyl, dialkyl-aminobenzylhaving 1-4 carbon atoms in each alkyl moiety, phenyl, naphthyl,halo-substituted phenyl, alkyl-phenyl having 1-4 carbon atoms in thealkyl moiety, nitro-phenyl, cyano-phenyl, trifluoromethyl phenyl, alkylchlorophenyl having 1-4 carbon atoms in the alkyl moiety trifluoromethylchloro phenyl, and furfuryl; R' is selected from the group consisting ofhydrogen, alkyl of 1-4 car bon atoms, alkenyl of 2-4 carbon atoms, andalkoxyalkyl having 1-4 carbon atoms in the alkoxy moiety and 1-4 carbonatoms in the alkyl moiety; R" is selected from the group consisting ofhydrogen, alkyl of 1-3 carbon atoms, and alkenyl of 2-3 carbon atoms;and R is selected from the group consisting of alkyl, alkenyl andalkynyl of up to 4 carbon atoms, and alkoxy of 1-4 carbon atoms.

2. Compound according to claim 1 wherein R is selected from the groupconsisting of hydrogen, C alkyl, C alkoxy, C alkyl, C cycloalkyl, Calkyl-C cycloalkyl, tri-(C alkyD-cyclohexenyl, tetrahydronaphthyl,fluorenyl, pheny1-C alkyl, naphthyl-C alkyl, diphenyl-methyl,triphenyl-methyl, monoto trichlorosubstituted benzyl, C alkyl phenyl Calkyl, C alkoxy benzyl, nitro benzyl, cyano-benzyl, trifluoromethylbenzyl, di-(C alkyl)-amino-benzyl, phenyl,

naphthyl, chloro phenyl, dichloro phenyl, bromophenyl, iodo phenyl,fluoro phenyl, C alkyl-phenyl, nitro phenyl, cyano phenyl,trifluoromethyl phenyl, (C alky1)-(chloro)-phenyl,(trifiuoromethyl)-(chloro)-phenyl, and furfuryl; R is selected from thegroup consisting of hydrogen, C, alkyl, C alkenyl, and C alkoxy-C alkyl;R" is selected from the group consisting of hydrogen, C alkyl, and Calkenyl, and R' is selected from the group consisting of C alkyl, Calkenyl, C alkynyl, and C alkoxy.

3. Compound according to claim 1 wherein R is selected from the groupconsisting of C alkyl, C cycloalkyl, C alkyl-C cycloalkyl,tetrahydronaphthyl, phenyl-C alkyl, naphthyl-C alkyl, diphenyl-methyl,chloro-benzyl, dichloro-benzyl, C alky1-phenyl-C alkyl, C alkoxy-benzyl,di-(C alkyl)-amino-benzyl, phenyl, chloro-phenyl, dichloro-phenyl, Calkyl-phenyl, nitro-phenyl, trifluoromethyl-phenyl, (Calkyl)-(chloro)-phenyl, (trifluoromethyl)-(chloro)-phenyl, and furfuryl,R is selected from the group consisting of C alkyl, C alkenyl, and Calkoxy-C alkyl, R" is selected from the group consisting of hydrogen, Calkyl, and C alkenyl, and R" is selected from the group consisting of Calkyl and C alkenyl.

4. Compound according to claim 1 wherein R is selected from the groupconsisting of C alkyl, C cycloalkyl, phenyl, chloro-phenyl, Calkyl-phenyl, and (trifluoromethyl)-(chloro)-phenyl, R is C alkyl, R" isselected from the group consisting of hydrogen and C alkyl, and R' isselected from the group consisting of C alkyl and C alkenyl.

5. Compound according to claim 1 wherein R is selected from the groupconsisting of C alkyl, cyclohexyl, phenyl, 2- and 4- chlorophenyl, 4-(Calkyl)-phenyl, and 4-trifluoromethyl-Z-chloro-phenyl, R' is C alkyl, Ris selected from the group consisting of hydrogen and C alkyl, and R'"is selected from the group consisting of C alkyl and allyl.

References Cited UNITED STATES PATENTS 3,121,089 2/1964 Itinsson26O306.8 3,454,591 7/1969 Schulz et al 260-306.8 A 3,551,442 12/ 1970Guillot et al 260306.8 R

RICHARD J. GALLAGHER, Primary Examiner US. Cl. X.R. 71-90 urm-m) 51m 125PA'I-EN'I 0mm;

CERTIFICATE OF CORRECTION p 5,801,589 Dated April 2, 197a Inventofls)KLAUS sAssE ET AL. (Pag 1 of It is certified that error appearsin theelbow-Identified patent and that said Letters Patent are herebycorrected as shown below:

r I n n I I Col, 33 11ne change I C m to C Col. 4, line 9, insert(comma) between "methyl" and "ethyl".

Col. 8, lin '59, correot formula to read as follows:

c --Nu C oIH I CI line Z QI CoInpou ncI (62) canoel 1- h1oro' and I sobsfifufe t h etefor l-[hf-(h' -ch l oro ---7. Co]... 11', lin ieCompound 222; ohange ,"3- z liih y l" to 3- mefhy1 Col Moo 66, Compound227 ,ohange"q-me tfi$ i!' to l-m ethyl Col; 11, 1in e"70, Compouod 230,correct -spe l l i ritg of "thiadiazoione". Col 21, 1in e 74, change'Iamveo 40% Col. 22, Example 7, Compound (139), correct formula to readas follows:

- I um I w slim us PA'IENI "0mm CERTIFICATE CORRECTION I Y 4* Patent:No. 3, 801,589 I t I Inventor) I I (Page 2 of 2 and cfifiaii iiiiiisQZLSZZZQRZiZEi;ZLZZZZf3ii Cols; 23, 24 'l ab'le 3 COmPOl H'ld (17) underheading "M.P. (C) c han ge "72-7" to 72-74 r I V C013. 31, 3 2,1ab1;e"3,Cpmpouhds (114) (115) (116) cancel "C H I' and substitute ehei'efer 13 11 I Compoupd (129) under heading R"' change "cH -cu-cu to cn-cn=cu I Signed and sealed this 7th day of January 1975.

(SEAL) Attest:

McCOY M. GIBSON JR. Attesting Officer I C. IfIAR-SHALL DANN Commissionerof' Patents

